CN101889034A

CN101889034A - Polymer

Info

Publication number: CN101889034A
Application number: CN2008801192957A
Authority: CN
Inventors: 维尔日妮·埃里克松; 马库·瓦赫泰里; 马里奥·韦内宁; 托马斯·加罗夫; 亚里·黑托宁; 彼得里·雷科宁; 西夫·博迪尔·弗雷德里克森; 卡特林·诺德-瓦豪格; 马里特·塞姆; 约鲁恩·尼尔森; 伊雷妮·赫兰
Original assignee: Borealis Technology Oy
Current assignee: Borealis Technology Oy
Priority date: 2007-12-05
Filing date: 2008-12-05
Publication date: 2010-11-17
Anticipated expiration: 2028-12-05
Also published as: EP2222732B1; WO2009071324A1; EP2222732A1; US8461280B2; US20110028665A1; CN101889034B; EP2067799A1

Abstract

A multimodal linear low density polyethylene polymer having a final density of 900 to 940 kg/m3, and containing at least one [alpha]-olefin comonomer in addition to ethylene comprising: (A) 30 to 60 wt% of a lower molecular weight component being an ethylene homopolymer or a copolymer of ethylene and at least one a-olefin; and (B) 70 to 40 wt% of a higher molecular weight component being a copolymer of ethylene and at least one [alpha]-olefin, said a-olefin being the same or different from any [alpha]-olefin used in component (A) but with the proviso that both components (A) and (B) are not polymers of ethylene and butene alone; wherein the multimodal LLDPE has a dart drop of at least 700 g; and wherein components (A) and (B) are obtainable using a Ziegler-Natta catalyst.

Description

Polymkeric substance

The present invention relates to be applicable to that production has the multimodal linea low density polymkeric substance of the film of excellent impact property, and relate to film and other goods by this polymer manufacture.This polymkeric substance can be used in the individual layer that forms unitary film or multilayer film, for example cast membrane (cast film) or blown film (blown film).The present invention relates to be used to produce the method for this polymkeric substance in addition and relate to polymkeric substance with some concrete improvement characteristic.

In the past during the decade, the market of linear low density polyethylene (LLDPE) develops rapidly.Present far-ranging LLDPE has been applied in injection moulding (or ejection formation), rotoforming, blow molding, pipe, pipeline and lead and the cable application.LLDPE has the skeleton of substantial linear, only has short chain branch, and normal length is about 3～10 carbon atoms.In LLDPE, ramose length and frequency, and density thus are controlled by the type of employed comonomer in the polymerization and the type of consumption and catalyzer.

Many LLDPE resins are typically introduced 1-butylene or 1-hexene as comonomer.More the resin that has remarkable strength advantage with respect to ethene/butene-1 copolymer is produced in the use of high-molecular weight alpha-olefin comonomer.Higher alpha-olefin comonomer in vogue in the commercial applications is 1-hexene, 4-methyl-1-pentene and 1-octene.The LLDPE major applications of Sheng Chaning is in the film product now, and wherein the excellent physical properties of LLDPE film and calendering (drawdown) characteristic makes it to be very suitable for the wide spectrum application.The feature of LLDPE film is generally excellent tensile strength, high limit elongation, good shock strength and excellent paracentesis resistance.

These performances, and toughness strengthen by improving molecular weight.Yet along with poly molecular weight increases, the workability of resin reduces usually.By the blend of polymkeric substance is provided, the performance of high molecular weight resin can be kept, and workability, especially extrudability (coming from lower-molecular-weight component) can be improved.

The blending of polymkeric substance can successfully realize in grading reactor is handled, as at United States Patent (USP) 5,047,468 and 5,126, describe in 398, although as above Zhi Bei original position blend and it is found that to have the advantageous feature of mentioning before this by the film of its production still industrially still continues to seek to have the film that is suitable for concrete application characteristic.

The film that WO03/066699 describes is formed by the blending of two kinds of polymeric constituent original positions, has wherein used metalloscene catalyst to produce polymkeric substance.This film allegedly has excellent sealing ability.

WO2005/014680 has further described original position multimodal LLDPE polymkeric substance, and this polymkeric substance is applicable to injection moulding.This polymkeric substance adopts metallocene catalyst once more and produces.

In EP-A-778289, described the two-stage series connection reactor for treatment and be used to generate multimodal polymer.Adopt ziegler-natta catalyzed, but LMW component homopolymer or be homopolymer basically typically.

In WO03/020821, multimodal LLDPE polymkeric substance has been described also.This LLDPE generally adopts the special geometry metalloscene catalyst that limits to be prepared, and is applied in the pipe production.

The inventor seeks new multimodal polymer and prepared therefromly has good especially impact property and can not weaken the film of workability.For example, this allows that formation has the strong film of lower Material Cost.This film also should have good tearing strength.

The inventor has prepared a kind of novel polymer now, and it has very high shock strength and good tearing strength, and it also has desirable workability.Good workability generally means higher output and lower energy requirement.

Therefore, by seeing on the one hand, the invention provides a kind of 900～940kg/m that has ³Final densities also contains the multimodal linear low-density polyethylene polymer of at least a alpha-olefin comonomer except that ethene, and it comprises:

(A) lower-molecular-weight component of 30wt%～60wt%, it is the multipolymer of Alathon or ethene and at least a alpha-olefin; With

(B) high molecular weight component of 70wt%～40wt%, it is the multipolymer of ethene and at least a alpha-olefin, described alpha-olefin is same or different from any alpha-olefin used in the component (A), but condition is component (A) and (B) all is not only the polymkeric substance of ethene and butylene;

Wherein multimodal LLDPE has the hammer falling impact strength of 700g (dart drop) (measuring according to following qualification) at least;

And component (A) and (B) all can adopt Ziegler-Natta catalyst to obtain wherein.Preferred described Ziegler-Natta catalyst contains at least the solid catalyst component by following compound formation:

(a) compound of periodictable 1～3 family;

(b) transistion metal compound of periodictable 4～10 families or actinium series or group of the lanthanides;

(d) compound of periodictable 13 families;

The catalyst component of wherein said Ziegler-Natta catalyst forms by emulsion/solidification method, and alternatively by following compound modified:

(c) one or more organic coordination compounds (ligand compounds), it is selected from the organic compound that contains the cyclopentadienyl anion skeleton.

On the other hand, the invention provides a kind of method that is used to produce previously described multimodal LLDPE, this method comprises:

Thereby polymerising ethylene and at least a alternatively alpha-olefin form the lower-molecular-weight component of 30wt%～60wt% in the fs; And

With the product of fs be transferred to subordinate phase and

Polymerising ethylene and at least a alternatively alpha-olefin are to form the high molecular weight component of 70wt%～40wt% in subordinate phase;

Component (A) and (B) all can adopt Ziegler-Natta catalyst to obtain wherein, this catalyzer preferably contain at least the solid-state ligand-modified catalyst component by following compound formation:

(a) compound of periodictable 1～3 family;

(d) compound of periodictable 13 families;

(c) one or more organic coordination compounds, it is selected from the organic compound that contains the cyclopentadienyl anion skeleton.

On the other hand, the invention provides a kind of composition that contains previously described multimodal linea low density polymkeric substance.

On the other hand, the invention provides a kind of goods that contain previously described multimodal linea low density polymkeric substance, preferred a kind of film.

On the other hand, the invention provides the purposes of previously described film aspect packing and the goods that adopt described film packing.

For fear of query, having at least, the multimodal polymer of 700g hammer falling impact strength is meant when described multimodal polymer is formulated as the film of thickness 40 μ m according to the scheme that proposes in membrane prepare embodiment, the film forming hammer falling impact strength of shape adopts ISO 7765-1, and (have dropping hammer of the hemispherical head of diameter 38mm drops on the film that is fixed on the hole from the height of 0.66m method " A ".If sample destroys, the weight of dropping hammer reduces, and if sample does not destroy, the weight increase.At least test 20 samples.Calculating causes 50% sample destructive weight) when measuring, obtain the value of 700g at least.

Above conditional request component (A) and (B) all be not only the polymkeric substance of ethene and butylene.In the time of when component (A) and (B) all containing butylene as comonomer, only possible is wherein in two components or another or this two also contain other alpha-olefin comonomer.Two components all can not be the polymkeric substance that ethene and butylene exist as only monomeric unit simply.

The performance of multimodal LLDPE

The present invention relates to have at least two kinds of components, the multimodal linear low density polyethylene of lower-molecular-weight component (A) and high molecular weight component (B).

Multimodal LLDPE polymkeric substance of the present invention should have 900～940kg/m ³, preferably less than 935kg/m ³, for example, 905-939kg/m ³, preferred 910～930kg/m ³In the scope, as 910～925kg/m ³Density, (ISO 1183-1:2004 " Immersion method ").

The MFR of multimodal LLDPE ₅At 0.05～10g/10min, preferred 0.1～5g/10min, for example, in the scope of 0.5～3g/10min, especially 0.8～3g/10min (1133,190 ℃/min of ISO, 5.0kg load).

The MFR of multimodal LLDPE ₂₁Should be 5～150, preferred 10～100g/10min, for example, in the scope of 15～70g/10min (1133,190 ℃/min of ISO, 21.6kg load).

The Mw of multimodal LLDPE should be 100,000～400, and 000, in preferred 130,000～300,000 the scope.Mn should be 5000～35, and 000, in preferred 8,000～25,000 the scope.The Mw/Mn of multimodal LLDPE should be 5～25, for example, and in 7～22 the scope.

Multimodal LLDPE of the present invention has lower xylene soluble fraction (XS).XS can be lower than 20wt%, according to measuring defined in the experimental section, for example, is lower than 15wt%, especially is lower than 10wt%.

Multimodal LLDPE can be by ethene together with at least a other alpha-olefin comonomer, preferred at least a C3-12 alpha-olefin comonomer, more preferably at least a C4-12 alpha-olefin comonomer, as, 1-butylene, 1-hexene or 1-octene form.The HMW component can contain at least a and the identical comonomer of used comonomer in the LMW component, but two kinds of components all can not only be the polymkeric substance of ethene and butylene.Two components all may be the polymkeric substance of ethene and hexene (or ethene and octene etc.), but should be understood that, even use identical comonomer in two kinds of components, two components also are different.For example, according to definition, the molecular weight of two components must be different.

Preferred comonomer combination comprises (LMW/HMW) butylene/hexene, hexene/butylene and hexene/hexene.

According to preferred embodiment, multimodal LLDPE is a trimer, that is, polymkeric substance contains ethene and two kinds of comonomers.Preferred HMW component contains used comonomer at least a LMW of the being different from component.In another embodiment that also has, the HMW component contains identical comonomer used in the LMW component, and contains in addition and be different from and preferably overweight comonomer used in the LMW component.

The amount of the comonomer that in multimodal LLDPE, exists, with respect to ethene, preferred generally 1wt%～20wt%, for example, 2wt%～15%wt%, especially 5wt%～13wt%.The 1-hexene content of preferred LLDPE of the present invention is lower than 8mol%.Ideally, the butene content of multimodal polymer of the present invention is lower than 5mol%, more preferably less than 4mol%, for example, passes through C ¹³NMR measures.

As noted above, multimodal LLDPE of the present invention contains lower-molecular-weight component (LMW) and high molecular (HMW) component at least.

Usually, polyethylene, for example, LLDPE composition (contain at least two kinds of polyethylene parts, it is normally produced under different polymerizing conditions and causes these parts to have difference (weight average) molecular weight and molecular weight distribution) is called as " multimodal ".Prefix " many " is meant the number of the different polymer moieties that exist in the polymkeric substance.Therefore, for example, multimodal polymer comprises so-called " bimodal " polymkeric substance is made up of two parts.The form of the molecular weight distribution curve of multimodal polymer such as LLDPE, that is, the polymer weight mark will demonstrate two or more maximum values as the curve outward appearance of its molecular weight function, or typically obviously widen than the curve of single component.For example, if polymkeric substance is produced in the successive multi-stage process, wherein adopt tandem reactor and use different condition in each reactor, the polymer moieties that produces in different reactor so will all have its molecular weight distribution and weight-average molecular weight separately.When the molecular weight distribution curve of this polymkeric substance was recorded, the single curve of these parts for the total polymer product that obtains, typically formed the molecular weight distribution curve of widening together.

The LMW component has the molecular weight lower than high molecular weight component.Preferably molecular weight exists at least 1000 between component, and preferably at least 5000, at least 20,000 difference especially.

Multimodal LLDPE of the present invention is preferably bimodal or three peaks, and is especially bimodal.

The LMW component

The lower-molecular-weight component of multimodal LLDPE preferably has at least 50, preferred 100g/10min at least, and preferred 110～3000g/10min, for example, the MFR of 110～500g/10min ₂The molecular weight of lower-molecular-weight component should be preferably 15,000～50, and 000, for example, in 20,000～40,000 the scope.

If the Mw/Mn of LMW component 3～10, for example, in 5～8 the scope, is preferred.

The density of lower-molecular-weight component can be at 930～980kg/m ³, for example, 940～970kg/m ³, preferred 945～965kg/m ³, 947～955kg/m especially ³Scope in.The density of LMW component is relatively low for multimodal polymer, is a feature of the present invention.

Lower-molecular-weight component should preferably account for 30wt%～60wt% of multimodal LLDPE, for example, and 30wt%～55wt%, especially 35wt%～50wt%, the most particularly 40wt%～48wt%.Therefore, if when the HMW component is the more component that exists, be preferred.

Lower-molecular-weight component can be Alathon (that is, therein ethylene is the monomer of only depositing), but especially wherein only there is a kind of comonomer in the optimal ethylene multipolymer.Especially be preferably the multipolymer of ethene and 1-butylene or 1-hexene.

Co-monomer content preferably keeps low as far as possible in the LMW component, because low co-monomer content it is found that not only relevant with the improvement of impact property, and relevant with the improvement of tearing strength in the LMW component.Co-monomer content is that the magnitude that is lower than 10wt% is suitable, preferably is lower than 8wt%, especially is lower than 3wt% and (passes through C ¹³NMR measures).

The HMW component

High molecular weight component should have lower density than lower-molecular-weight component.

The density that high molecular weight component should have is lower than 915kg/m ³, for example, be lower than 913kg/m ³, preferably be lower than 912kg/m ³, especially be lower than 910kg/m ³The HMW component has low-down density, is a feature of the present invention.

Therefore this property combination it is believed that the workability of having improved polymkeric substance of the present invention, makes it, and for example, is easy to extrude on film production line (film line) and can improves the output of film production line.

The Mw of high molecular weight component can be 100,000～1, and 000,000, in preferred 150,000～500,000 the scope.

If the Mw/Mn of HMW component 3～10, for example, in 5～8 the scope, then is preferred.

High molecular weight component accounts for 70wt%～40wt% of multimodal LLDPE, for example, and 68wt%～45wt%, more preferably 67wt%～50wt%, especially 65wt%～52wt%.

High molecular weight component is ethylene copolymer preferably, especially copolymer (that is, wherein only having a kind of comonomer) or trimer (having two kinds of comonomers).

Especially preferred HMW component is the copolymer of ethene and hexene or the trimer of ethene, 1-butylene and 1-hexene or 1-octene.In preferred embodiment, the HMW component contains non-existent alpha-olefin at least a LMW component.So another preferred embodiment in when the LMW component is a kind of homopolymer, the HMW component contains the comonomer of at least 2 kinds of alpha-olefins.

The amount of the comonomer that exists in the HMW component can be at 1～6wt%, for example, and in the scope of 2wt%～5wt%, especially 3wt%～5wt%.Should be noted that, the amount of comonomer can not directly be measured (in a technology in the HMW component, wherein the second stage of HMW component in multi-stage process forms), but can be based on the amount of the amount of existing LMW component and final polymkeric substance and to the understanding of product shunting (production split) and calculate.

Other components of multimodal polymer

Multimodal LLDPE can contain other polymeric constituents except that LMW and HMW component.For example, polymkeric substance can contain the polyethylene prepolymer (can be obtained by prepolymerization step well-known in the art) up to 10wt%.Under the situation of this prepolymer, pre-polymer component can be contained in one of LMW and HMW component, and preferred LMW component as above limits.Yet,, be preferred if do not adopt prepolymerization step.

Other performances

Polymkeric substance of the present invention is measured according to method described below has very high hammer falling impact strength.Therefore, for the 40 μ m films of the present invention according to the description among following film blowing embodiment preparation, hammer falling impact strength F50 (ISO 7765/1) can be 700g at least, preferred 750g at least, more preferably 800g, 900g especially at least at least.The hammer falling impact strength value that polymkeric substance more of the present invention have surpasses 1000g.

In another embodiment, hammer falling impact strength F50 value is that any film more than the 10 μ m should be 700g at least for the thickness of polymer formation of the present invention.

In another embodiment, the ratio of hammer falling impact strength F50 value and film thickness should be 17.5g/ μ m at least, preferably 20g/ μ m, more preferably 22.5g/ μ m, especially 25g/ μ m at least.

Therefore, on the other hand, multimodal linear low-density polyethylene polymer provided by the invention has 900～940kg/m ³Final densities, and contain at least a alpha-olefin comonomer except that ethene, this polymkeric substance comprises:

Wherein the hammer falling impact strength F50 value that has of multimodal LLDPE should be 17.5g/ μ m at least with respect to film thickness,

And component (A) and (B) all can adopt Ziegler-Natta catalyst to obtain wherein.

Multimodal LLDPE polymkeric substance of the present invention also has excellent tearing strength, especially in the vertical (machine direction, axial or fiber direction).Therefore, for the thick film of the present invention 40 μ m according to the description among following film blowing embodiment preparation, the tearing strength on machine direction can be 1N at least, preferably 1.5N, 2N especially at least at least.

Produce

Multimodal LLDPE polymkeric substance, for example, generally can be by two-stage or multistage polymerization or by using two or more different Ziegler-Natta catalysts in the single-stage polymerization, to prepare.Yet, importantly guarantee high and lower-molecular-weight component closely mixing before extruding.This most advantageously realizes by using multi-stage process.

Preferred multimodal LLDPE produces in the two-stage polymerization, wherein all uses identical Ziegler-Natta catalyst in two steps.The two-stage polymerization can be carried out in two different reactors in a reactor or for example.Under the situation of back, for example, can adopt two slurry-phase reactors or two Gas-phase reactor.Yet preferred multimodal LLDPE adopts slurry polymerization then to adopt vapour phase polymerization in Gas-phase reactor in annular-pipe reactor and prepares.

Annular-pipe reactor-liquid-gas phase reactor system is sold as the BORSTAR reactor assembly by Borealis.Any multimodal LLDPE of the present invention is preferably comprising that the first slurry loop polymerization then is to form in the two-stage approach of vapour phase polymerization.

Used condition is well-known in this method.For slurry-phase reactor, temperature of reaction will be generally in the scope of 60～110 ℃ (for example, 85-110 ℃), reactor pressure will be generally at 5～80bar (for example, scope 50-65bar), and the residence time will be generally in 0.3～5h (for example, scope of 0.5～2h).Used thinner will generally be the aliphatic hydrocarbon of boiling point-70～+ 100 ℃ of scopes.In this reactor, if desired, polymerization can be carried out under super critical condition.Slurry polymerization also can be implemented in the body (bulk) that reaction medium is formed by polymerization single polymerization monomer.

For Gas-phase reactor, used temperature of reaction will generally (for example, 70～110 ℃ in) the scope, reactor pressure will be general in the scope of 10～25bar, and the residence time will be generally 1～8 hour at 60～115 ℃.Gases used normally non-reactive gas such as nitrogen or low boiling hydrocarbon such as propane are together with monomer (for example, ethene).

Preferably, the low-molecular weight polymer part is produced in the annular-pipe reactor of operate continuously, therein ethylene at (one or more) comonomer (if desired), ziegler-natta polymerization catalysts together with conventional promotor, the i.e. compound of the 13rd family's metal, as Al alkylate and chain transitive agent (chain transfer agent) as polymerization under the existence of hydrogen.Thinner is the inertia aliphatic hydrocarbon typically, preferred Trimethylmethane or propane.Preferred C4/C2 ratio is 200～600mol/kmol in the first step.

The hydrogen charging can be the magnitude of 50～150g/h.

High molecular weight component can adopt identical catalyzer to form in Gas-phase reactor subsequently.

Ratio between two kinds of components has importance.Although the HMW component of higher concentration improves hammer falling impact strength, when the ratio of HMW component is too high, will more difficultly control the method for producing polymkeric substance.High hammer falling impact strength value (split ratio) under conventional LMW/HMW splitting ratio can realize that also this is a feature of the present invention.

When the HMW component in multistage polymerization as second when preparation step, it is impossible directly measuring its performance.Yet, for example, for polymerization process of the present invention described above, the density of HMW component, MFR ₂Deng adopting Kim McAuley equation to calculate.Therefore, density and MFR ₂Can both pass through document K.K.McAuley and J.F.McGregor:On-line Inference of Polymer Properties in an IndustrialPolyethylene Reactor, AIChE Journal, June 1991, Vol.37, No, 6, pages 825-835 and determining.By McAuley equation 37 bulk densities, wherein the density after the final densities and first reactor is known.MFR ₂Calculate by McAuley equation 25, wherein calculate final MFR ₂With the MFR after first reactor ₂

The all components of multimodal LLDPE of the present invention preferably adopts the Ziegler-Natta catalyst preparation, and this catalyzer contains solid-state, the ligand-modified catalyst component that is made of following compound at least:

(a) compound of periodictable 1～3 family

(b) transistion metal compound of periodictable 4～10 families or actinium series or group of the lanthanides

(c) one or more organic coordination compounds, it is selected from the organic compound that contains the cyclopentadienyl anion skeleton, and

(d) compound of the periodic table of elements 13 families;

The catalyst component of wherein said Ziegler-Natta catalyst forms by emulsion/solidification method.

Although belong to the single component that the interior different catalysts of this definition all can be used for forming multimodal LLDPE, should be appreciated that, preferably use identical catalyzer to form this two kinds of components.

Generally speaking, in producing this type catalyst, do not use external carrier (externalsupport).

The organic ligand of Ziegler-Natta catalyst (c) is derived from has the anionic compound of organic ligand.Cationic moiety is metal preferably, i.e. these compounds metal-salt of organic anion preferably.Metal is the metal of 1 or 2 families preferably, preferred Mg and Li metal, and the compound that promptly is used for the catalyst ligand modification is anionic Li of organic ligand or Mg salt preferably.

The organic ligand negatively charged ion comprises the cyclopentadienyl hydrocarbon skeleton, and it can comprise heteroatoms such as N, P, O, S etc.

Described cyclopentadienyl hydrocarbon skeleton can be a part that condenses the hydrocarbon loop systems.Example as such loop systems, can mention, for example, pentalene base (pentalenyl), indenyl, Azulene base (atsulenyl), Dicyclopentadiene (DCPD) and phenyl (indasenyl), acenaphthenyl (asenaphtylenyl) or fluorenyl (fluorenyl) compound.All hydrocarbon skeletons can be that replace or unsubstituted form.For example, the organic ligand negatively charged ion can be to replace or unsubstituted cyclopentadienyl, replacement or unsubstituted indenyl or replacement or unsubstituted fluorenyl compounds.

Optional one or more substituting groups, preferably be independently selected from halogen, alkyl such as C1-20-alkyl, C2-20-thiazolinyl, C2-20-alkynyl, C3-12-cycloalkyl, C6-20-aryl or C7-20-aralkyl, in loop section, contain 1,2,3 or 4 heteroatomic C3-12-cycloalkyl, C6-20-heteroaryl, C1-20-haloalkyl ,-SiR " ₃,-OSiR " ₃,-SR " ,-PR " ₂Or-NR " ₂, each R " and be hydrogen or alkyl independently, for example, C1-20-alkyl, C2-20-thiazolinyl, C2-20-alkynyl, C3-12-cycloalkyl or C6-20-aryl; Or for example ,-NR " ₂Situation under, two substituent R " can form ring together with the nitrogen-atoms that is attached thereto, for example, five-or six-ring.

The anionic example of organic ligand comprises ring polyene-based (cyclopolyenyls) with 5～24 carbon atoms or the ring polyene-based that replaces, as cyclopentadienyl, methyl cyclopentadienyl, the ethyl cyclopentadienyl, tertiary butyl cyclopentadienyl, the hexyl cyclopentadienyl, the octyl group cyclopentadienyl, 1,2-dimethyl cyclopentadienyl, 1,3-dimethyl cyclopentadienyl, 1,2,4-trimethylammonium cyclopentadienyl, 1,2,3,4-tetramethyl-ring pentadienyl, the pentamethyl-cyclopentadienyl, indenyl, 4-methyl isophthalic acid-indenyl, 4,7-dimethyl indenyl, 4,5,6, the 7-tetrahydro indenyl, fluorenyl or methylfluorenyl, 2, the 3-dimethyl-dimethyl-tertiary butyl-siloxanes cyclopentadienyl.

The specific examples of useful Mg and Li coordination compound has dicyclopentadienyl Mg, cyclopentadienyl Li, indenyl Li, 3,4-dimethyl-tertiary butyl-siloxanes cyclopentadienyl and fluorenyl Li coordination compound.The Li part is preferred, especially indenyl Li.

The mol ratio of part and transition metal component (b) is 0.03～5 in the preferred catalyst, more preferably 0.05～3, be more preferably 0.07～2, especially 0.2～0.6 or 0.25～1.2.

In preferred embodiment, compound in Ziegler-Natta catalyst (b) is the transistion metal compound (IUPAC) of 4～6 families in the periodictable.Preferred transition metal component (b) is selected from Ti, Hf or Zr, and most preferably it is Ti.Particularly preferably be, this Ti compound is a halogenated titanium, more preferably tetrachloro Ti.

Component (a) is magnesium compound preferably, and for example, with the complex compound (complex) of alkoxyl group, ether, alkyl and/or halogen group, any hydrocarbyl group that wherein exists in complex compound is C preferably _1-20Hydrocarbon residue, for example, C _1-15Group, preferred C _3-10Group is as C _4-8Group, for example, alkyl, aryl, aralkyl or alkaryl straight chain, cyclic or side chain, straight or branched alkyl suitably, preferred branched-chain alkyl, as 2-ethyl-1-hexyl or ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, it replaces with halogen alternatively.

Component (d) is the compound of 13 family's metals, preferably organic aluminide, and more preferably aluminium alkyl halide, aluminum alkyls and alkoxy aluminum compound preferably have formula Al (alkyl) _xCl _3-xThe Al compound, wherein alkyl is to have 1～12, preferred 1～8, the more preferably alkyl of 1～6 C atom, and 0＜x＜3, preferred x is 1.

For example using in Preparation of catalysts except above-claimed cpd, properties-correcting agent etc. also is possible, for example, catalyst compound can be with combinations such as dissimilar ether, ester, silicon ethers and further activity of such catalysts and/or selectivity is carried out modification, and this is known in this area.

By compound (a) and (b) at least and (d) and the catalyst component that forms by coordination compound (c), be prepared with emulsion/solidification method, as what in the WO 03/106510 of Borealis, disclose generally, for example, according to the guidance that in its claim, provides.

Except the above-mentioned catalyst component (a)～(d) of catalyzer, catalyst system for example comprises, promotor previously discussed.Promotor is the alkylate of 13 family's metals routinely, as al-alkyl compound.

(one or more) promotor is fed to separately in the actual polymerization procedure usually.Promotor typically is in excess in the transition metal of transistion metal compound and uses.For example, when using aluminum alkyls as promotor, the mol ratio of transition metal is 1～500mol/mol in aluminium in the promotor and the transition metal component, preferred 2～100mol/mol, more preferably 5～50mol/mol, especially 5～30mol/mol.

In highly preferred embodiment, use TIBA (triisobutyl aluminium) or TEA (triethyl aluminum) as promotor.Most particularly use TIBA.Find that surprisingly when using TIBA, the HMW component that forms has significantly low density in gas phase, and whole polymkeric substance is than adopting other promotors to obtain higher hammer falling impact strength.

Emulsion/the solidification method of catalyst system therefor preferably includes among preparation the present invention:

Preparation compound (a) and (b) and common solution (common solution) (d) or contain the compound (a) and (b) and (d) in one or more the solution that separates;

Described (one or more) solution is scattered in its unmixing and with respect to described compound is in the inert solvent, obtaining emulsion, wherein said (one or more) solution is to contain the compound (a) and (b) and drop form (d) forms disperse phase;

Curing catalysts compound in the dispersive drop; And

The coordination compound (c) that one or more is selected from the organic compound that contains the cyclopentadienyl anion skeleton at any preparatory phase before the curing schedule, during or afterwards, but in the end join in the disperse phase before the recycling step.

Compound (c) preferably together with the compound (a) and (b) or any kind (d) add.

Such catalyzer is disclosed among the EP application No 06014743.6 in detail, and it is as a reference incorporated herein.

Alternatively, the curing catalysts compound particle that is obtained can reclaim.Before can in the end reclaiming, washes the curing catalysts particle.

This method makes it possible to produce has highly preferred morphology, for example, has the active catalyst particle of predetermined spherical form and homogeneous granules distribution of sizes, and need not to use the outside porous support material of any interpolation, as inorganic oxide, for example, silicon-dioxide.And can obtain required surface property.

In the preferred method that forms catalyst component, compound (a) and (b), (c) and (d) can join in a kind of solution that is scattered in immiscible solvent, or alternately, can prepare at least two kinds of independent solution of every kind or the described compound of part, it is scattered in the immiscible solvent successively subsequently.

Term " is in the inert solvent at unmixing with it and with respect to described compound ", in this article refers to the described solvent that forms external phase and chemically is being inertia under the used condition (for example, temperature) at least during dispersion steps.The solvent of preferred described external phase does not contain the compound (a) and (b), (c) of the formation catalyzer of any significant quantity of dissolved wherein or (d).Therefore, rigid granules is to form with the drop form by the compound that is derived from disperse phase (that is, being provided in to be dispersed in the emulsion in the solution in the external phase).

Two-phase and heterogeneous system contained in term used herein " emulsion ".

As previously discussed, before final recycling step, solid catalyst particle can wash.The solid particulate of flushing can separate with dry to obtain described dry granules solid catalyst in mode known in the art.Another possibility is that this can be used in polymerization equally with solid catalyst particle furnishing slurry and obtain catalyzer-oil-slurry after washing to the oily liquids.Oily liquids comprises oil, oil or hydrocarbon or its mixture, preferred hydrocarbon ils, and as white oil, this is the mixture of alkane and naphthenic hydrocarbon.

According to preferred embodiment, the method preparation of the catalyst component of Ziegler-Natta catalyst of the present invention by may further comprise the steps:

The solution of preparation compound (a);

Preparation compound (d) and solution (c);

The solution of described two solution with compound (b) is mixed;

(a) and (b), (c) and the mixing solutions (d) of described acquisition is scattered in it unmixing and is in the inert solvent and obtains the emulsion that wherein said solution forms disperse phase with respect to described compound;

Curing catalysts component in the dispersive drop;

Wash the solidified granules of catalyst alternatively; With

Alternatively with recovered in solid form solidified granules of catalyst.

In the preferred implementation in all preparation alternative, before in the end reclaiming, washes granules of catalyst.

In preferred embodiment, the solvent of described formation external phase is an inert solvent, comprise halogenated organic solvent or its mixture, the preferred fluorinated organic solvent, especially partly fluoridize, height is fluoridized or perfluorination organic solvent and functional derivative thereof, this is meant that described solvent can contain other functional groups and/or other halogens such as chlorine, bromine and/or iodine.

The example of above-mentioned solvent be partly fluoridize, height is fluoridized or perfluorinated hydrocarbon, as alkane, alkene and naphthenic hydrocarbon, ether such as perfluor ether and amine is tertiary amine especially, and functional derivative.Preferably partly fluoridize, height is fluoridized or fluoridized, perfluorinated hydrocarbon especially, for example, as C3-C30, as the perfluoroparaffin of C4-C10.The suitable perfluoro alkane and the specific examples of perfluorinated cycloalkanes comprise perflexane, PF 5070, PFO and perfluor (methylcyclohexane).Half fluorinated hydrocarbons relates in particular to partly fluoridizes normal alkane, as perfluoroalkyl-alkane.

" partly fluoridize " hydrocarbon and also comprise such hydrocarbon, wherein-C-F and-C-H unit (blocks) alternately." height is fluoridized " is meant that great majority-quilt-C-F unit, C-H unit replaces." perfluorination " be meant all-the C-H unit is all replaced by-C-F unit.Referring to A.Enders and the G.Maas paper at " Chemie in unserer Zeit ": 34.Jahrg.2000, Nr.6, and ofPierandrea Lo Nostro in " Advances in Colloid and Interface Science; 56 (1995) 245-287, Elsevier Science.

Emulsion can form by any method known in the art: by mixing, as by solution as described in the violent stirring to as described in the solvent of formation external phase or by means of mixing roll, or by means of ultrasonic wave, or by using so-called phase-change method it is transferred to two-phase system forms drop and prepare emulsion by changing system temperature subsequently by at first forming homogeneous system.

During emulsion forms step and curing schedule, for example keep the two-phase state by suitable stirring.

In addition, emulsifying agent/emulsion stabilizer can use, and preferably uses in a manner known in the art, and helps to form the stability of emulsion and/or emulsion.For described purpose, for example, tensio-active agent, for example, based on hydrocarbon (comprise molecular weight, for example, up to 10000 and the polymer hydrocarbon of using (one or more) heteroatoms to interrupt alternatively) type, preferred halohydrocarbon, for example be selected from as partly fluoridizing or high fluorinated hydrocarbons, having alternatively ,-OH ,-SH, NH ₂,-COOH ,-COONH ₂, cyclic ethers and/or any reactive derivatives of these groups such as the functional group of alkoxyl group or alkyl-carboxylic acid ester group, or, preferably have partly the fluoridizing of functionalized end-, height fluoridizes-or perfluorinated hydrocarbon, can use.

Alternately, the tensio-active agent precursor that emulsification and/or emulsion-stabilizing auxiliary agent also can be by will containing at least a functional group reacts and forms with described functional group being had reactive behavior and be present in catalyst solution or form compound in the solvent of external phase.The reaction product that is obtained plays actual emulsion adjuvant and/or the function of stabilizer in the emulsion system of forming.

The example that is applicable to the tensio-active agent precursor that forms described reaction product comprises, for example, known tensio-active agent, this tensio-active agent has at least a group, described group be selected from as-OH ,-SH, NH2 ,-COOH ,-COONH ₂, have the cyclic ethers of 3～5 annular atomses and/or any derivatives reactivity such as the alkoxyl group or the alkyl-carboxylic acid ester group of these groups; For example, having partly the fluoridizing of one or more described functional groups, height fluoridizes-or perfluorinated hydrocarbon.Preferably, the tensio-active agent precursor has terminal functionality as defined above.

Be contained in the catalyst solution with the compound preferred package of this tensio-active agent precursors reaction, and can be the other additive or the compound of one or more formation catalyzer.This compound for example is, compound of 13 families (for example, with undefined compound (d)) and/or transistion metal compound (for example, with undefined compound (b)).

In preferred embodiment, high fluorizated C1-n (C4-30-or C5-15 suitably) alcohol (for example, highly fluorinated enanthol, octanol or nonyl alcohol) is joined in compound (a), compound (b), (d) and/or the solution (c) and form " actual " tensio-active agent.The step of this adding is preferably implemented afterwards in be scattered in the solvent that forms external phase with undefined compound (a), (c), (d) and solution (b).

Yet, these and any other additive, and/or compound, if desired, can both be in any stage adding system of dispersion and/or curing schedule.

Solidifying (one or more) catalyst component in dispersant liquid drop can implement according to variety of way, for example, and by impelling or quicken to form the formation of the described solid catalyst of the reaction product that has compound in the drop.This is with or without the outside stimulus effect according to used compound and/or required solidification rate, changes as system temperature, all can implement.

The curing catalysts particle can pass through washing step.The particulate droplet profile can be maintained substantially.The particle that forms can have at 1～500 μ m, and for example, 5～500 μ m advantageously are the median size in 5～200 μ m or 10～150 mu m ranges.Even the median size of 5～60 μ m all is possible.According to the polyreaction of applications catalyst, can select particle diameter.Advantageously, particle is a spheric basically, and they have low porosity and low surface area.

The various possibilities of compound and combination all belong to those skilled in that art's technical ability category.

(a) and (d) and (c) form solution and can for example, implement under 20～80 ℃ the temperature at 0～100 ℃.Preferably, compound (b) is at lesser temps, and for example 0～30 ℃ adds down.Dispersion steps can be at 0～100 ℃, for example, and at about 0～70 ℃, as implementing down at 0～30 ℃.

In aforesaid each preparation method, compound (a) and (b) and (d) can add with mol ratio known in the art, for example the mol ratio of the element of the element of compound (d) such as Al and compound (a) such as Mg can be 0.3: 1～3: 1, for example, 0.5: 1～2: 1, the element of the element of compound (b) such as Ti and compound (a) such as the mol ratio of Mg can be 3: 1～0.1: 1, for example, and 2: 1～0.2: 1.

In one embodiment, liquid catalyst is by contacting dialkyl magnesium compound (for example, dialkyl magnesium is as butyl octyl-Mg (BOMAG)) and alcohol roh (wherein R for alkyl) as defined above to be prepared as 2-ethyl-1-hexanol.Adding structural formula in this solution is Al (R) _xX _3-xAluminum compound (wherein R, X and x as above define, and preferred Al alkyl halide (for example, muriate) is as, EtAlCl ₂, in this solution, add coordination compound as defined above) and in the solution that obtains, add titanium compound, as TiCl ₄Under situation about Al and Ti compound all being joined in the Mg-ROH complex compound, then preferred Al compound and coordination compound at first add.Solution can contain other aforesaid solvents, and for example, aliphatics or aromatic solvent are as normal heptane or toluene.Described solution can form under 10～50 ℃ temperature, preferably forms under 10～30 ℃ envrionment temperature.The solution that is obtained is scattered in the immiscible solvent by mixing then, for example is scattered in the perfluoroparaffin of above definition.Mix and compatibly at room temperature carry out, still, for example, lesser temps or elevated temperature also can adopt.

In the dispersion that is obtained, add emulsifying agent as defined above, fluoridize or fluoridized hydrocarbon as height, and improve/formation of stabilization drop with sense end.The curing of catalyst component is preferably by at 1～180min in drop, for example, 1～90 or 5～30min in improve the temperature of mixture gradually, for example, be increased to 100 ℃ from room temperature, for example, implement to 60～90 ℃.The size that depends on reactor heat-up time.

In an embodiment that also has, alkyl magnesium, as above definition with ROH reaction as defined above, is preferably reacted in a kind of solvent such as toluene, and with aluminum compound, as aluminum alkyl halide, for example, EtAlCl ₂, be preferably dissolved in a kind of solvent such as the toluene, add to form first solution with coordination compound, this solution is scattered in inert solvent, in the perfluoroparaffin as above definition.In the disperse phase that is obtained, separately add TiCl ₄Solution.Adding TiCl ₄Afterwards, the drop of disperse phase solidifies to be implemented by heating as mentioned above, and the solidified catalyzer washes alternatively and reclaims as mentioned above.Wherein separately add TiCl ₄This embodiment be preferred embodiment.Other inert solvents also can be used in the formation of described solution as defined above.

During curing schedule (wherein, curing schedule is preferably at about 60～80 ℃, preferably under about 70～80 ℃, carry out), can be preferably except that desolvating and washing solid with rinse solution alternatively, this rinse solution can be any solvent or solvent mixture, as those solvents above definition and/or used in the art, preferred hydrocarbons, as pentane, hexane or heptane, suitable is heptane.Catalyzer after the flushing can carry out drying or can size mixing in oil and use as catalyzer-oily slurry in polymerization process.

Generally speaking, in final solid catalyst particle, the mol ratio of Mg: Ti can for, for example, 10: 1～1: 10, preferred 7: 1～1: 5, more preferably 6: 1～1: 3.The mol ratio of Ti: Al can for, for example, 10: 1～1: 4, preferred 5: 1～1: 3, more preferably 3: 1～1: 2.And, contacting under the situation about preparing with pure by alkyl magnesium at compound (a), the mol ratio of Mg^1 OH is suitably at 1: 1～1: 4, for example, and 1: 1～1: 3.5, between 1: 1.5～1: 3.1.

The use of this catalyst substance is favourable in the present invention, has good particle form because catalyzer has high reactivity and polymkeric substance can be formed.And catalyzer is suitable for preparing polymkeric substance of the present invention, wherein needs the extreme splitting ratio under the specific density.Catalyzer generally seems to allow to carry out polymerization under wideer processing window (processing window).

Composition

Multimodal polymer of the present invention can with other polymeric constituents, for example, LDPE, LLDPE component or HDPE mixed with polymers and form the composition that contains polymkeric substance of the present invention.Two kinds of combination of polymers of the present invention are mixed and prepared highly preferred composition also is possible.Yet, preferably do not have other polymeric constituents, and multimodal polymer of the present invention be used to produce film (or layer of film) polymeric constituent only arranged.Yet, polymkeric substance can with the additive of routine such as antioxidant, UV stablizer, acid scavenger, nucleator, release agent and polymer processing agent (PPA) form composition.

Film forms and character

Polymkeric substance of the present invention can be the form of powder or spherolite, the form of preferred spherolite.Spherolite by tradition extrude, granulation or attrition techniques obtain and be the ideal form of polymkeric substance of the present invention, because they can directly join in the converting machine (converting machinery).Spherolite is different from polymer powder, and particle diameter is lower than 1mm in polymer powder.

The use of spherolite guarantees that composition of the present invention can be by transforming film forming to transforming the simple online adding spherolite of machine, for example, and unitary film.

For adopting polymeric blends to form film, different polymeric constituents must extrude and cast/closely to mix before the blown film be very important because as can not closely mix and just exist in the danger that occurs inhomogeneity in the film, as, gel.

Polymkeric substance of the present invention it is found that, allows to form the film with desirable balance performance.They have excellent mechanical property and are easy to processing.Particularly, these films have high hammer falling impact strength, high tearing strength, stopping property and good workability.

Film of the present invention is preferably unitary film or film of the present invention and is used to form one deck in the multilayer film.Any film of the present invention can have 10～250 μ m, preferred 20～200 μ m, for example, 30～150 μ m, more preferably for example, 30～135 μ m, or the thickness of 30～60 μ m.

Can utilize in the simple online adding forcing machine of polymkeric substance spherolite and produce film of the present invention.For adopting polymeric blends to form film, different polymeric constituents extrude with blown film before closely to mix be very important because otherwise can have the danger that occurs inhomogeneity in the film, as, gel.Therefore, especially preferred, for example, adopt twin screw extruder, preferred incorgruous rotation forcing machine extrude with film blowing before thoroughly mix these components.Screw design by the selective membrane forcing machine makes it to be designed to well blend and homogenizes, and also can obtain enough uniformities.

Film of the present invention can carry out blowing or casting, preliminary election blowing.Blown film will typically be extruded by annular die and produce, and be blow molded into pipe-shaped membrane by forming the foam that caves between roll after the curing.This film carries out otch, cutting or conversion (for example, dress gusset (gusseted)) as required subsequently.Traditional film production technology can be used according to this respect.Typically said composition will be extruded under 160～240 ℃ temperature, and by the frost line height of 1 or 2 to 8 times of die orifice diameters is provided 10～50 ℃ of (generally being air) coolings of blowing down.The blowing ratio should be generally 1.5～4, for example, 2～4, preferred 2.5～3 scope.

Film of the present invention also can be a cast membrane.The cast membrane method relates to and forms thin, fusion thin plate or film by slit or concora crush punch die with fused is polymer-extruded.This film be by from the gas percussion of air knife or vacuum box (vaccum box) and " button " on cooling roller (the typically roller of water cooling and chromium coating) surface.Film is annealed immediately and produced its edge notch (edges slit) subsequently before clot.Because short annealing step, cast membrane generally have better optical property than blown film, and can produce with high linear speed more.

Film of the present invention has high hammer falling impact strength and tearing strength, especially on machine direction.In the process of following, will provide some parameter based on concrete film thickness.This is because the variation on the film thickness causes the size variation of the parameter be concerned about.In order to obtain quantitative value, therefore need provide concrete film thickness.This does not also mean that the present invention do not contain other film thicknesses, and is meant that when with given thickness preparation, film should have given parameter value.

Therefore, for the present invention's 40 μ m films of producing according to the description of following examples parts, hammer falling impact strength F50 (ISO 7765/1) can be 700g at least, preferred 750g at least, more preferably 800g, 900g especially at least at least.The hammer falling impact strength that some polymkeric substance of the present invention have surpasses 1000g.

In another embodiment, hammer falling impact strength F50 value for any film with the above thickness of 10 μ m by polymer formation of the present invention, should be 700g at least.

Elmendorf tearing strength on machine direction for the 40 μ m films of producing according to the description of following examples parts, can be 1.5N at least.

Film of the present invention, for example, unitary film can be laminated on the blocking layer (barrier layer) according to mode known in the art.For food and medical applications, for example, with the blocking layer, that is, water oxygen is layer thoroughly, and being incorporated into perhaps is necessary in the membrane structure.This can adopt traditional lamination to be achieved.Suitable blocking layer is known, comprises polymeric amide, ethylene vinyl alcohol, PET and metallization Al layer.

Therefore, on the other hand, the invention provides a kind of contain will be before this laminated product (laminate) of film lamination to the blocking layer of definition.

In this embodiment, can easily barrier layer be depressed on two unitary films as previously described, form the 3-tier architecture that the blocking layer constitutes the middle layer thus.

Film of the present invention has various widely application, but is especially receiving publicity aspect the packing of food and drink, consumer goods and industrial goods, medicine equipment and the heavily loaded packing.Concrete application comprises industrial liner, the packing bag of heavy burden shipping, shopping bag, bread bag and freezer bag.

Other application

Polymkeric substance of the present invention also can be applied to rotational moulding shaping, injection molded, blow molding, extruding coating and pipeline and form.

The present invention will be described with further reference to following non-limiting example now:

Analytical test

Following method is used for measuring the character that above generality limits and following examples limit.The material and the membrane sample that are used for measuring and limiting are prepared according to the description of concrete grammar and form.

Density

Density of material is measured according to ISO 1183-1:2004 " Immersion method ".

MFR

Load 2.16,5 and 21.6kg measure MFR2/5/21 respectively under 190 ℃ according to ISO 1133.

Hammer falling impact strength

Shock strength (g/50%) is measured according to hammer falling impact strength (Dart-drop).Hammer falling impact strength adopts ISO 7765-1, and method " A " is measured.Dropping hammer has the hemispherical head of 38mm diameter, falls on the film that is fixed on the hole from the height of 0.66m.If sample destroys, the weight of dropping hammer just reduces, and if sample is not destroyed, the weight increase.At least test 20 samples.Calculating causes 50% sample destructive weight.

Film used in this test is made according to the description in following examples part.Film thickness is 40 μ m.

Tearing strength (tearing (N) according to elmendorf measures)

Tearing strength adopts ISO 6383/2 method to measure.Adopt pendulum instrument (pendulum device) to measure and to tear the required power of whole membrane sample of propagating.Pendulum vibrates by certain radian under gravity, tears sample from advance otch seam.Sample is fixed on one side by pendulum and the other side is fixed by retaining clip.Tearing strength is exactly to tear the required power of sample.Tearing strength (N/mm) calculates divided by film thickness by tearing strength subsequently relatively.

Molecular weight, molecular weight distribution (Mn, Mw, MWD)

Mw/Mn/MWD measures according to following method by gel permeation chromatography (GPC):

Weight-average molecular weight Mw and molecular weight distribution (MWD=Mw/Mn, wherein Mn be number-average molecular weight and Mw is a weight-average molecular weight) measure according to ISO 16014-4:2003 and ASTM D6474-99.Waters GPCV2000 instrument, be equipped with RI-detector and in-line viscometer, adopt 2 * GMHXL-HT and 1 * G7000HXL-HT TSK-gel column and 1 of Tosoh Bioscience, 2,4-trichlorobenzene (TCB, with 250mg/L 2,6-di-t-butyl-4-methyl-phenol is stable) as solvent under 140 ℃, 1mL/min measures with constant flow rate.Each injection 209.5 μ L sample solutions of analyzing.Column device adopts pervasive correction (universal calibration) (according to ISO 16014-2:2003) to proofread and correct in the scope of 1kg/mol～12000kg/mol with polystyrene (PS) standard of at least 15 narrow MWD.According to the use MarkHouwink constant of being given among the ASTM D 6474-99.All samples by with 0.5～4.0mg polymer dissolution in keeping maximum 3h in the highest 160 ℃ of gentle continuously down vibrations among the stabilization TCB of 4mL (under 140 ℃) (identical) and before being sampled in the GPC instrument with moving phase.

Xylene soluble part (XS) content

In 135 ℃ under agitation with the 2.0g polymer dissolution in the 250mL p-Xylol.Behind 30min, solution is at room temperature cooled off 15min, make it precipitate 30min down subsequently at 25 ℃.Solution is filtered with filter paper in two 100mL flasks.

Solution in first 100mL container under nitrogen gas stream, volatilize and resistates 90 ℃ of following vacuum-dryings until reaching constant weight.

XS％＝(100×m×v ₀)/(m ₀×v)

m ₀=initial polymer amount (g)

M=resistates amount (g)

v ₀=original volume (ml)

The volume of v=analytic sample (ml)

Nuclear magnetic resonance of carbon ( ¹³C-NMR) spectrum-co-monomer content

¹³C-NMR analyzes the content that is used for the working sample comonomer.Sample by will about 0.350g polymkeric substance and the 2.0mL dissolution with solvents in the 10mmNMR pipe, prepare.Solvent is 1,2,90/10 mixture of 4-trichlorobenzene and benzene-d6.By under 150 ℃ in heat block (heating block) heating tube and its content dissolve and the sample that homogenizes.

(proton-decoupled carbon-13 monopulse NMR spectrum of Overhauser effect (or Ovshinsky nuclear effect, nuclear Overhauseeffect) is recorded on the Joel ECX 400MHzNMR spectrograph to have NOE.The acquisition parameter that is used to test comprises that 45 ° of flip angles, 4 vacations sweep (dummy scans), 3000 transitions and 1.6s acquisition time, 20kHz spectrum width, 125 ℃ of temperature, WALTZ uncouple (decoupling) and 6.0s relaxation delay (relaxation delay).Used processing parameter comprises the zero filling of 32k data point and adopts the change mark of exponential window function, widens then at the 1.0Hz simulated line and manually make zero (manual neroth) and first step phase correction and baseline correction automatically.

Co-monomer content adopts to adopt from handling the integration rate that spectrogram obtains and is described in JC.Randall works (JMS-Rev.Macromol.Chem.Phys., C29 (2﹠amp; 3), the assignment among the 201-317 (1989), adopt following formula to calculate:

E＝(\αB+\αH+\βB+\βH+\γB+\γH+\δ++)/2

B=(methyne B+2B+1B)/3

H=(methyne H+4H+3H+2H)/4

Wherein methyne is the carbon potential point of CH branch sites, α, β, γ, contiguous CH, i.e. CH, α, β, γ, δ δ.δ ++ be a large amount of (bulk) CH2 site, and 1,2,3 and 4 sites are represented along each carbon potential point of ramose, methyl is designated 1.

CE＝100％*E/(E+B+H)

CB＝100％*B/(E+B+H)

CH＝100％*H/(E+B+H)

Cloud point-ASTM D1003

Film used in this test is prepared according to following description in the embodiment part.Film thickness is 40 μ m.

Embodiment 1

Preparation of Catalyst:

Catalyzer 1

The Mg-complex compound forms: 40kg BOMAG (butyl octyl magnesium, the 20wt% colloidal sol in toluene) is fed in the reactor.Slowly add 12.4kg 2-Ethylhexyl Alcohol (2-EHA, dry on molecular sieve).The EHA/Mg mol ratio is 2.Temperature of reaction keeps below 45 ℃.Solution mixing 30min also is cooled to room temperature.

Aluminium/ligand solution preparation:

6.5kg EADC (ethylaluminium dichloride) is fed in the metal drum.0.173kg indenyl Li (powder) is slowly added and mixes (by vibration) so that obtain dissolving fully.

Preparation of catalysts

With 12L PFC ((perfluor-1,3-dimethyl cyclohexane), on molecular sieve dry)) and the 0.06L tensio-active agent ((3-(perfluoro capryl)-1,2 epoxy prapane (propenoxide), 97wt% solution) adding reactor also at room temperature mixes with 450RPM.

In independent container, add the as above 1.5L Mg complex compound of preparation, and slowly in the Mg complex compound, add 0.58L aluminium/ligand solution (prepared product as described above) and under 450RPM, mix 30min.After this mixes, complex solution is transferred in the container that contains the PFC/ tensio-active agent.Mixing velocity remains on 450Rpm.Behind 15min, add 0.053L TiCl then ₄After the adding, mixture stirs 15min.

Emulsion heats under 75 ℃ and mix 1h under this temperature.After 75 ℃ of following precipitated catalyst 30min, remove PFC.Catalyzer washes twice with 50 ℃ of heptane of 14L.In the end after the flushing, remove heptane and add some primary oils (primoil) subsequently and acquisition oil bag catalyst slurry.

Polymerization

Implement polymerization in two-stage process, this two-stage process comprises that the slurry loop polymerization then is vapour phase polymerization.

The following polymeric fs (first step) in the presence of the quantitative ethene of table 1 middle finger, comonomer, propane and hydrogen in 500dm ³Implement in the annular-pipe reactor.Temperature is 85 ℃.Catalyzer and promotor directly are added in the annular-pipe reactor.With the solution of promotor TEA ((or TIBA, if mention) with 10wt% in heptane) further make the ultimate density of acquisition between 1wt%～2wt% with the propane dilution.Calculate the promotor inlet amount and keep the Al/Ti ratio of 20mol/mol.

The polymkeric substance that will contain active catalyst is separated from reaction medium and is transferred in the Gas-phase reactor of 20 bar pressures and 85 ℃ of following operations, wherein adds other ethene, hydrogen and comonomer, and its consumption is also described in table 1.

After gas phase, make the polymkeric substance degassing and be transferred to forcing machine.

Film blowing is used for the mensuration of hammer falling impact strength and Elmendorf tearing strength

Adopt polymer formation film of the present invention.

Use forcing machine 25d on the unitary film line, die orifice diameter 250mm and die orifice gauge (die gauge) 1.5mm carries out blowing 40 μ m thick film (by the polymer formation of being discussed).Blow-up ratio is 2.5: 1, and frost line height, FLH, 600mm.The temperature distribution scope is 180～210 ℃.

Claims

1. a multimodal linear low-density polyethylene polymer has 900～940kg/m ³Final densities, and contain at least a alpha-olefin comonomer except that ethene, described polymkeric substance contains:

(A) lower-molecular-weight component of 30wt%～60wt% is the multipolymer of Alathon or ethene and at least a alpha-olefin; With

(B) high molecular weight component of 70wt%～40wt%, multipolymer for ethene and at least a alpha-olefin, any alpha-olefin used in described alpha-olefin and the component (A) is identical or different, but condition is component (A) and (B) all is not only the polymkeric substance of ethene and butylene;

Wherein, described multimodal LLDPE has the hammer falling impact strength of 700g at least;

And component (A) and (B) can adopt Ziegler-Natta catalyst to obtain wherein.

2. polymkeric substance according to claim 1, wherein said Ziegler-Natta catalyst contain at least the ingredient of solid catalyst by following compound formation:

(a) compound of periodictable 1～3 family;

(d) compound of periodictable 13 families;

The catalyst component of wherein said Ziegler-Natta catalyst is formed by emulsion/curing, and alternatively by following compound modified:

(c) one or more organic coordination compounds are selected from the organic compound that contains the cyclopentadienyl anion skeleton.

3. according to the described polymkeric substance of aforementioned each claim, the final densities of wherein said polymkeric substance is 910～925kg/m ³

4. according to the described polymkeric substance of aforementioned each claim, the scope of the molecular weight distribution of wherein said polymkeric substance is 7～22.

5. according to the described polymkeric substance of aforementioned each claim, the hammer falling impact strength of wherein said polymkeric substance is 900g at least.

6. according to the described polymkeric substance of aforementioned each claim, the 35wt%～48wt% of the described polymkeric substance of wherein said LMW ingredients constitute, and the 65wt%～52wt% of the described polymkeric substance of described HMW ingredients constitute.

7. method that is used to produce according to the described multimodal LLDPE of aforementioned each claim comprises:

At fs polymerising ethylene and at least a alternatively alpha-olefin and form the lower-molecular-weight component of 30wt%～60wt%; And

With the product of fs be transferred to subordinate phase and

At subordinate phase polymerising ethylene and at least a alpha-olefin and form the high molecular weight component of 70wt%～40wt%;

Wherein, component (A) and (B) can adopt Ziegler-Natta catalyst and obtain.

8. method according to claim 7, wherein said Ziegler-Natta catalyst contain at least the solid-state ligand-modified catalyst component by following compound formation:

(a) compound of periodictable 1～3 family;

(d) compound of periodictable 13 families;

Wherein, the described catalyst component of described Ziegler-Natta catalyst forms by emulsion/solidification method, alternatively by following compound modified:

9. method according to claim 8, wherein said method is implemented in the presence of promotor, and described promotor is TIBA.

10. a composition contains each described multimodal linea low density polymkeric substance in the with good grounds claim 1～6.

11. goods, preferred a kind of film contains each described multimodal linea low density polymkeric substance in the with good grounds claim 1～6.

12. film according to claim 11 has the hammer falling impact strength of 700g at least,

For example when on the film of the 40 μ m that describe production according to this paper, measuring.